To realise molecular scale electrical operations beyond the von Neumann bottleneck, new types of multi-functional switches are needed that mimic selflearning or neuromorphic computing by dynamically toggling between multiple operations that depend on their past. Here we report a molecule that switches from high to low conductance states with massive negative memristive behaviour that depends on the drive speed and number of past switching events, with all measurements fully modelled using atomistic and analytical models. This dynamic molecular switch (DMS) emulates synaptic behaviour and Pavlovian learning, all within a 2.4 nm thick layer that is three orders of magnitude thinner than a neuronal synapse. The DMS provides all fundamental logic gates necessary for deep learning because of its time-domain and voltage-dependent plasticity. The synapse-mimicking multi-functional DMS represents adaptable molecular scale hardware operable in solid-state devices opening a pathway to simplify dynamic complex electrical operations encoded within a single ultra-compact component.
Control over the energy level alignment in molecular junctions is notoriously difficult, making it challenging to control basic electronic functions such as the direction of rectification. Therefore, alternative approaches to control electronic functions in molecular junctions are needed. This paper describes switching of the direction of rectification by changing the bottom electrode material M = Ag, Au, or Pt in M−S(CH 2 ) 11 S−BTTF//EGaIn junctions based on self-assembled monolayers incorporating benzotetrathiafulvalene (BTTF) with EGaIn (eutectic alloy of Ga and In) as the top electrode. The stability of the junctions is determined by the choice of the bottom electrode, which, in turn, determines the maximum applied bias window, and the mechanism of rectification is dominated by the energy levels centered on the BTTF units. The energy level alignments of the three junctions are similar because of Fermi level pinning induced by charge transfer at the metal−thiolate interface and by a varying degree of additional charge transfer between BTTF and the metal. Density functional theory calculations show that the amount of electron transfer from M to the lowest unoccupied molecular orbital (LUMO) of BTTF follows the order Ag > Au > Pt. Junctions with Ag electrodes are the least stable and can only withstand an applied bias of ±1.0 V. As a result, no molecular orbitals can fall in the applied bias window, and the junctions do not rectify. The junction stability increases for M = Au, and the highest occupied molecular orbital (HOMO) dominates charge transport at a positive bias resulting in a positive rectification ratio of 83 at ±1.5 V. The junctions are very stable for M = Pt, but now the LUMO dominates charge transport at a negative bias resulting in a negative rectification ratio of 912 at ±2.5 V. Thus, the limitations of Fermi level pinning can be bypassed by a judicious choice of the bottom electrode material, making it possible to access selectively HOMO-or LUMO-based charge transport and, as shown here, associated reversal of rectification.
Redox-active molecular junctions have attracted considerable attention because redox-active molecules provide accessible energy levels enabling electronic function at the molecular length scales, such as, rectification, conductance switching, or molecular transistors. Unlike charge transfer in wet electrochemical environments, it is still challenging to understand how redox-processes proceed in solid-state molecular junctions which lack counterions and solvent molecules to stabilize the charge on the molecules. In this minireview, we first introduce molecular junctions based on redox-active molecules and discuss their properties from both a chemistry and nanoelectronics point of view, and then discuss briefly the mechanisms of charge transport in solidstate redox-junctions followed by examples where redoxmolecules generate new electronic function. We conclude with challenges that need to be addressed and interesting future directions from a chemical engineering and molecular design perspectives.
Directional excitation of surface plasmon polaritons (SPPs) by electrical means is important for the integration of plasmonics with molecular electronics or steering signals toward other components. We report electrically driven SPP sources based on quantum mechanical tunneling across molecular double-barrier junctions, where the tunneling pathway is defined by the molecules' chemical structure as well as by their tilt angle with respect to the surface normal. Self-assembled monolayers of S(CH 2 ) n BPh (BPh = biphenyl, n = 1−7) on Au, where the alkyl chain and the BPh units define two distinct tunnel barriers in series, were used to demonstrate and control the geometrical effects. The tilt angle of the BPh unit with respect to the surface normal depends on the value of n, and is 45°when n is even and 23°when n is odd. The tilt angle of the alkyl chain is fixed at 30°and independent of n. For values of n = 1−3, SPPs are directionally launched via directional tunneling through the BPh units. For values of n > 3, tunneling along the alkyl chain dominates the SPP excitation. Molecular level control of directionally launching SPPs is achieved without requiring additional on-chip optical elements, such as antennas, or external elements, such as light sources. Using the molecular tunneling junctions, we provide the first direct experimental demonstration of molecular double-barrier tunneling junctions.
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